U.S. patent application number 11/205832 was filed with the patent office on 2006-02-23 for fire-protection coating.
This patent application is currently assigned to Clariant GmbH. Invention is credited to Achim Hennemann, Volker Thewes.
Application Number | 20060041042 11/205832 |
Document ID | / |
Family ID | 35149589 |
Filed Date | 2006-02-23 |
United States Patent
Application |
20060041042 |
Kind Code |
A1 |
Thewes; Volker ; et
al. |
February 23, 2006 |
Fire-protection coating
Abstract
The invention relates to a fire-protection coating which forms
an insulating layer, which comprises a flame retardant mixture
which comprises a phosphorus/nitrogen flame retardant and comprises
a phosphinic salt of the formula (I) and/or comprises a
diphosphinic salt of the formula (II) and/or comprises polymers of
these, ##STR1## where R.sup.1, R.sup.2 are identical or different
and are C.sub.1-C.sub.6-alkyl, linear or branched, and/or aryl;
R.sup.3 is C.sub.1-C.sub.10-alkylene, linear or branched,
C.sub.6-C.sub.10-arylene, -alkylarylene or -arylalkylene; M is Mg,
Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K
and/or a protonated nitrogen base; m is from 1 to 4; n is from 1 to
4 and x is from 1 to 4.
Inventors: |
Thewes; Volker; (Erftstadt,
DE) ; Hennemann; Achim; (Hofheim, DE) |
Correspondence
Address: |
CLARIANT CORPORATION;INTELLECTUAL PROPERTY DEPARTMENT
4000 MONROE ROAD
CHARLOTTE
NC
28205
US
|
Assignee: |
Clariant GmbH
|
Family ID: |
35149589 |
Appl. No.: |
11/205832 |
Filed: |
August 17, 2005 |
Current U.S.
Class: |
524/115 |
Current CPC
Class: |
C08K 5/0066 20130101;
C08K 2201/014 20130101; C09D 5/185 20130101; C08K 5/5313
20130101 |
Class at
Publication: |
524/115 |
International
Class: |
C08K 5/49 20060101
C08K005/49 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 17, 2004 |
DE |
10 2004 039 758.9 |
Claims
1. A fire-protection coating which forms an insulating layer,
comprising a flame retardant mixture wherein the flame retardant
mixture includes a phosphorus/nitrogen flame retardant and a
phosphinic salt of the formula (I) a diphosphinic salt of the
formula (II) a polymer of the phosphinic salt, a polymer of the
diphosphinic salt, or a mixture thereof, ##STR4## wherein R.sup.1,
R.sup.2 are identical or different and are C.sub.1-C.sub.6-alkyl,
linear or branched, or aryl; R.sup.3 is C.sub.1-C.sub.10-alkylene,
linear or branched, C.sub.6-C.sub.10-arylene, -alkylarylene or
-arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi,
Sr, Mn, Li, Na, K or a protonated nitrogen base; m is from 1 to 4;
n is from 1 to 4 and x is from 1 to 4.
2. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein the phosphorus/nitrogen flame retardant
is a nitrogen-containing phosphate of the formulae (NH4)y H3-y
PO.sub.4 or (NH4 PO3)z, where y is from 1 to 3 and z is from 1 to
10 000.
3. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein the phosphorus/nitrogen flame retardant
is ammonium hydrogenphosphate, ammonium dihydrogenphosphate,
ammonium polyphosphate, or a mixture thereof.
4. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein the phosphorus/nitrogen flame retardant
is an ammonium polyphosphate of the formula
(NH.sub.4PO.sub.3).sub.n, where n is a number from 10 to
.ltoreq.1000.
5. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein the phosphorus/nitrogen flame retardant
is the reaction products of melamine with phosphoric acid or
condensed phosphoric acids, the reaction products of condensates of
melamine with phosphoric acid or with condensed phosphoric acids,
or a mixture of thereof.
6. The fire-protection coating which forms an insulating layer, as
claimed in claim 5, wherein the phosphorus/nitrogen flame retardant
is melam, melem, melon, dimelamine phosphate, dimelamine
pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine
polyphosphate, melam polyphosphate, melon polyphosphate, melem
polyphosphate, mixed polysalts thereof or mixtures thereof.
7. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein the ratio, by weight, of the
phosphorus/nitrogen flame retardant to the phosphinic salt of the
formula (I), the diphosphinic salt of the formula (II), the polymer
of the phosphinic salt, the polymer of the diphosphinic salt or
mixtures thereof is from 0.1 to 100 to 100 to 0.1.
8. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein the ratio, by weight, of the
phosphorus/nitrogen flame retardant to the phosphinic salt of the
formula (I), the diphosphinic salt of the formula (II), the polymer
of the phosphinic salt, the polymer of the diphosphinic salt or
mixtures thereof is from 1 to 50 to 50 to 1.
9. The fire-protection coating which forms an insulating layer, as
claimed in claim 1 comprising: A) from 1 to 99% by weight of an
epoxy resin, B) from 1 to 99% by weight of the flame retardant
mixture, and C) from 0 to 60% by weight of an additive.
10. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, comprising: A) from 10 to 90% by weight of an
epoxy resin, B) from 2 to 60% by weight of a the flame retardant
mixture, and C) from 3 to 45% by weight of an additive.
11. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, comprising A) from 30 to 85% by weight of an
epoxy resin, B) from 3 to 50% by weight of the flame retardant
mixture, and C) from 5 to 40% by weight of an additive.
12. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, further comprising from 0 to 60% by weight of
at least one additive selected from the group consisting of
accelerators, fillers, auxiliaries, blowing agents, nitrogen
synergists, carbon donors, pigments, flexibilizers, reactive
diluents and mixtures thereof.
13. (canceled)
14. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein M is calcium, aluminum, or zinc.
15. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein R.sup.1 and R.sup.2 are identical or
different and are methyl, ethyl, n-propyl, isopropyl, n-butyl,
tert-butyl, n-pentyl, or phenyl.
16. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein R.sup.3 is methylene, ethylene,
n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene,
n-octylene, n-dodecylene; phenylene, naphthylene; methylphenylene,
ethylphenylene, tert-butylphenylene, methylnaphthylene,
ethylnaphthylene, tert-butylnaphthylene; phenylmethylene,
phenylethylene, phenylpropylene, or phenylbutylene.
17. The fire-protection coating which forms an insulating layer, as
claimed in claim 4, wherein n is a number from 200 to
.ltoreq.1000.
18. A substrate coated with the fire-protection coating which forms
an insulating layer, as claimed in claim 1.
19. The substrate as claimed in claimed 18, wherein the substrate
is a floorcovering, molding, wall, load-bearing metallic structure
or a non-load-bearing metallic structure.
Description
[0001] The present invention is described in the German priority
application No. 10 2004 039 758.9, filed 17.08.2004, which is
hereby incorporated by reference as is fully disclosed herein.
[0002] The invention relates to a fire-protection coating which
forms an insulating layer and is based on substances which in the
event of a fire form a foam layer and carbonize, and on
film-forming binders, on blowing agents, and on conventional
auxiliaries and additives.
[0003] A feature of fire-protection coatings which form an
insulating layer, also termed intumescent coatings, is that in the
event of a fire they foam on exposure to an appropriate
temperature, and that this foaming of the abovementioned
fire-protection coating prevents, or at least inhibits, transfer of
heat to steel structures, ceilings, walls, cables, pipes, and the
like.
[0004] U.S. Pat. No. 4,965,296 describes a flame-retardant material
which is composed of a flame-retardant coating material and of an
electrically conductive material. The flame-retardant coating
material here is composed of substances which form foam and
carbonize, of a compound which generates gas, of a film-forming
binder, and of appropriate solvents. Other conventional ingredients
may optionally be present.
[0005] U.S. Pat. No. 4,879,320 describes a similar flame-retardant
composition to which, instead of a conductive material, a ceramic
fiber material has been added.
[0006] U.S. Pat. No. 6,096,812 describes an intumescent coating
based on epoxy resins and having a particularly low specific
density of the dried film.
[0007] These coatings are mainly used to protect ships, oil
platforms, and other equipment for storage and processing of
inflammable hydrocarbons. This equipment generally requires a large
amount of fire-protection material in order to ensure adequate
insulation of the metallic components. This automatically leads to
a significant increase in the weight imposed upon the structures to
be protected. However, the additional weight imposed on the
load-bearing and non-load-bearing metal structures is often subject
to limits (e.g. on oil platforms).
[0008] The aim of the abovementioned fire-protection coatings of
the prior art is to achieve maximum fire resistance times with
minimum application quantities.
[0009] One approach to smaller application quantities can be
achieved by way of a reduction in the specific density of the dried
film (U.S. Pat. No. 6,096,812). A disadvantage is that there is
often an attendant reduction in fire-protection performance.
[0010] An overall disadvantage with the abovementioned
fire-protection coatings is that the foam structures formed in the
event of a fire do not permit any improvement in insulating effect,
and that the reaction does not begin until temperatures
T.gtoreq.180.degree. C. have been reached.
[0011] Indeed, in many cases the reaction does not begin until
temperatures relatively far above this threshold have been
reached.
[0012] It is therefore an object of the invention hereinafter to
provide fire-protection coatings which achieve longer
fire-resistance times for an identical application quantity, or
achieve identical fire-resistance times for a reduced application
quantity, when comparison is made with the prior art.
[0013] This object is achieved via a fire-protection coating whose
reaction begins at temperatures T<180.degree. C. (i.e. below
180.degree. C.).
[0014] The invention therefore provides a fire-protection coating
which forms an insulating layer, which comprises a flame retardant
mixture which comprises a phosphorus/nitrogen flame retardant and
comprises a phosphinic salt of the formula (I) and/or comprises a
diphosphinic salt of the formula (II) and/or comprises polymers of
these, ##STR2## where [0015] R.sup.1, R.sup.2 are identical or
different and are C.sub.1-C.sub.6-alkyl, linear or branched, and/or
[0016] aryl; [0017] R.sup.3 is C.sub.1-C.sub.10-alkylene, linear or
branched, C.sub.6-C.sub.10-arylene, -alkylarylene or [0018]
-arylalkylene; [0019] M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr,
Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogen base; [0020]
m is from 1 to 4; n is from 1 to 4 and x is from 1 to 4.
[0021] The phosphorus/nitrogen flame retardants are preferably
nitrogen-containing phosphates of the formulae (NH.sub.4).sub.y
H3-y PO4 or (NH4 PO.sub.3)z, where y is from 1 to 3 and z is from 1
to 10 000.
[0022] The phosphorus/nitrogen flame retardants are particularly
preferably ammonium hydrogenphosphate, ammonium
dihydrogenphosphate, and/or ammonium polyphosphate.
[0023] The phosphorus/nitrogen flame retardants are preferably
ammonium polyphosphate of the formula (NH.sub.4PO.sub.3).sub.n,
where n is a number from 10 to .ltoreq.1000, preferably from 200 to
.ltoreq.1000.
[0024] Other preferred phosphorus/nitrogen flame retardants are
reaction products of melamine with phosphoric acid or with
condensed phosphoric acids, or are reaction products of condensates
of melamine with phosphoric acid or with condensed phosphoric
acids, or are a mixture of these products.
[0025] The phosphorus/nitrogen flame retardants are particularly
preferably melam, melem, or melon, dimelamine phosphate, dimelamine
pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine
polyphosphate, melam polyphosphate, melon polyphosphate, and/or
melem polyphosphate, or are mixed polysalts thereof.
[0026] The inventive fire-protection coating which forms an
insulating layer preferably comprises the phosphorus/nitrogen flame
retardant and the phosphinic salt of the formula (I) and/or
comprises the diphosphinic salt of the formula (II) and/or
comprises polymers of these, in a ratio by weight of from 0.1 to
100 (phosphorus/nitrogen flame retardant) to from 100 to 0.1
(phosphinic salt).
[0027] The inventive fire-protection coating which forms an
insulating layer preferably comprises the phosphorus/nitrogen flame
retardant and the phosphinic salt of the formula (I) and/or
comprises the diphosphinic salt of the formula (II) and/or
comprises polymers of these, in a ratio by weight of from 1 to 50
(phosphorus/nitrogen flame retardant) to from 50 to 1 (phosphinic
salt).
[0028] The inventive fire-protection coating which forms an
insulating layer preferably comprises [0029] A) from 1 to 99% by
weight of an epoxy resin, and [0030] B) from 1 to 99% by weight of
a flame retardant mixture which comprises a phosphorus/nitrogen
flame retardant and comprises a phosphinic salt of the formula (I),
and/or comprises a diphosphinic salt of the formula (II), and/or
comprises polymers of these, [0031] C) from 0 to 60% by weight of
other additives.
[0032] The inventive fire-protection coating which forms an
insulating layer particularly preferably comprises [0033] A) from
10 to 90% by weight of an epoxy resin, and [0034] B) from 2 to 60%
by weight of a flame retardant mixture which comprises a
phosphorus/nitrogen flame retardant and comprises a phosphinic salt
of the formula (I), and/or comprises a diphosphinic salt of the
formula (II), and/or comprises polymers of these, [0035] C) from 3
to 45% by weight of other additives.
[0036] The inventive fire-protection coating which forms an
insulating layer also particularly preferably comprises [0037] A)
from 30 to 85% by weight of an epoxy resin, and [0038] B) from 3 to
50% by weight of a flame retardant mixture which comprises a
phosphorus/nitrogen flame retardant and comprises a phosphinic salt
of the formula (I), and/or comprises a diphosphinic salt of the
formula (II), and/or comprises polymers of these, [0039] C) from 5
to 40% by weight of other additives.
[0040] The inventive fire-protection coating which forms an
insulating layer in particular also comprises from 0 to 60% by
weight of additives, such as accelerators, fillers, auxiliaries,
blowing agents, nitrogen synergists, carbon donors, pigments,
flexibilizers, and/or reactive diluents, and also, if appropriate,
other additives. The total of the entirety of the components here
always amounts to 100% by weight.
[0041] M is preferably calcium, aluminum, or zinc.
[0042] It is preferable that R.sup.1 and R.sup.2 are identical or
different and are methyl, ethyl, n-propyl, isopropyl, n-butyl,
tert-butyl, n-pentyl, and/or phenyl.
[0043] It is preferable that R.sup.3 is methylene, ethylene,
n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene,
n-octylene, or n-dodecylene; phenylene or naphthylene;
methylphenylene, ethylphenylene, tert-butylphenylene,
methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene;
phenylmethylene, phenylethylene, phenylpropylene, or
phenylbutylene.
[0044] Protonated nitrogen bases are preferably the protonated
bases of ammonia, melamine, and triethanolamine, in particular
NH.sub.4.sup.+.
[0045] It is particularly preferable that R.sup.1 and R.sup.2 are
identical or different and are methyl, ethyl, n-propyl, isopropyl,
n-butyl, tert-butyl, n-pentyl, and/or phenyl.
[0046] The halogen-free epoxy compounds used according to the
invention (hereinafter also termed polyepoxy compounds) may be
saturated or unsaturated compounds, and may also be aliphatic,
cycloaliphatic, aromatic, and/or heterocyclic compounds. They may
moreover contain substituents which do not give rise to any
problematic side reactions under the mixing conditions or reaction
conditions, examples being alkyl substituents, aryl substituents,
ether groups, or the like. It is also possible to use mixtures of
various polyepoxy compounds. The average molecular weight Mn of
these polyepoxy compounds can be up to about 9000, but is generally
from about 150 to 4000.
[0047] By way of example, these polyepoxy compounds are
polyglycidyl ethers based on polyhydric, preferably dihydric,
alcohols, phenols, hydrogenation products of these phenols, and/or
on novolaks (reaction products of mono- or polyhydric phenols, such
as phenol and/or cresols, with aldehydes, in particular
formaldehyde, in the presence of acidic catalysts), these being
obtained in a known manner, e.g. via reaction of the respective
polyols with epichlorohydrin.
[0048] Examples which may be mentioned here of polyhydric phenols
are: resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane
(bisphenol A), isomer mixtures of dihydroxydiphenylmethane
(bisphenol F), 4,4'-dihydroxydiphenylcyclohexane,
4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4-dihydroxybiphenyl,
4,4'-dihydroxy-benzophenone, 1,1-bis(4-hydroxyphenyl)ethane,
1,1'-bis(4-hydroxyphenyl)isobutane,
2,2-bis(4-hydroxy-tert-butylphenyl)propane,
bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene,
tris(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl) 1,1'-ether.
[0049] Preference is given here to bisphenol A and bisphenol F.
[0050] Other suitable polyepoxy compounds are the polyglycidyl
ethers of polyhydric aliphatic alcohols. Examples which may be
mentioned of these polyhydric alcohols are 1,4-butanediol,
1,6-hexanediol, polyalkylene glycols, glycerol, trimethylolpropane,
2,2-bis(4-hydroxycyclohexyl)propane and pentaerythritol.
[0051] Other polyepoxy compounds which may be used are
(poly)glycidic esters obtained via reaction of epichlorohydrin or
of similar epoxy compounds with an aliphatic, cycloaliphatic, or
aromatic polycarboxylic acid, e.g. oxalic acid, adipic acid,
glutaric acid, phthalic acid, isophthalic acid, terephthalic acid,
tetrahydrophthalic acid, or hexahydrophthalic acid, or
naphthalene-2,6-dicarboxylic acid, or dimerized fatty acids.
Examples here are diglycidyl terephthalate and diglycidyl
hexahydrophthalate.
[0052] It is also advantageous in some cases to use polyepoxy
compounds which contain the epoxy groups randomly distributed
across the molecular chain and which can be prepared via emulsion
copolymerization, using olefinically unsaturated compounds
containing these epoxy groups, e.g. glycidyl esters of acrylic or
methacrylic acid.
[0053] Examples of other polyepoxy compounds which may be used are
those based on heterocyclic ring systems, e.g. hydantoin epoxy
resins, triglycidyl isocyanurate, and/or its oligomers,
triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenyl ether,
tetraglycidyldiaminodiphenylmethane, tetraglycidyidiaminodiphenyl
ether, tetrakis(4-glycidoxyphenyl)ethane, urazole epoxides, uracil
epoxides, oxazolidinone-modified epoxy resins, and polyepoxides
based on aromatic amines, such as alanine, e.g.
N,N-diglycidylaniline, diaminodiphenylmethane, and
N,N'-dimethylaminodiphenylmethane or N,N'-dimethylaminodiphenyl
sulfone. Other suitable polyepoxy compounds are described in
"Handbook of Epoxy Resins" by Henry Lee and Kris Neville,
McGraw-Hill Book Company, 1967, in the monograph by Henry Lee
"Epoxy Resins" American Chemical Society, 1970, in Wagner/Sarx,
"Lackkunstharze" [Synthetic Paint Resins], Carl Hanser Verlag
(1971), 5th edition, pp. 174-196 in "Angew. Makromol. Chemie", Vol.
44 (1975), pp. 151-163, in DE-A-27 57 733 and in EP-A-0 384 939,
which are incorporated herein by way of reference.
[0054] Preferred polyepoxide compounds are bisglycidyl ethers based
on bisphenol A, bisphenol F or bisphenol S (reaction products of
these bisphenols with epichloro(halo)hydrin) or oligomers of these,
polyglycidyl ethers of phenol-formaldehyde and/or
cresol-formaldehyde novolaks, or diglycidyl esters of phthalic,
isophthalic, terephthalic, tetrahydrophthalic and/or
hexahydrophthalic acid or of trimellitic acid, N-glycidyl compounds
of aromatic amines or of heterocyclic nitrogenous bases, such as
N,N-diglycidylaniline, N,N,O-triglycidyl-p-aminophenol, triglycidyl
isocyanurate or N,N,N',N-tetraglycidyl-bis(p-aminophenyl)methane,
hydantoin epoxy resins or aracid epoxy resins or di- or
polyglycidyl compounds of polyhydric aliphatic alcohols, such as
1,4-butanediol, trimethylolpropane or polyalkylene glycols.
Oxazolidinone-modified epoxy resins are also suitable. Compounds of
this type are already known (see: "Angew. Makromol. Chem., Vol. 44
(1975), pp. 151-163, and U.S. Pat. No. 3,334,110); the reaction
product of bisphenol A diglycidyl ether with diphenylmethane
diisocyanate (in the presence of a suitable accelerator) may be
mentioned as an example.
[0055] The polyepoxy resins may be present individually or in a
mixture during the preparation of the inventive fire-protection
coating. Hardener components which may be used are aliphatic and
aromatic polyamines. Aromatic polyamines are described by way of
example in EP-A-0 274 646. They are prepared via trimerization of
2,6- or 2,4-diisocyanatoalkylbenzenes, and subsequent hydrolysis of
the remaining isocyanate groups. These hardener components may be
used individually or in a mixture. These mixtures are available
industrially, and permit low-cost preparation of the hardener
component.
[0056] Heterocyclic polyamines having urea groups can be used as
further additive hardener component (i.e. in addition to the actual
hardener). The hardener mixture may also use not more than 30% of
other aromatic polyamines, such as 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl sulfone, and/or other heterocyclic
polyamines.
[0057] Preferred other additives present in the inventive
fire-protection coating are accelerators, fillers, auxiliaries,
blowing agents, nitrogen synergists, carbon donors, pigments,
flexibilizers, and/or reactive diluents.
[0058] Accelerators which may be used are especially imidazole
derivatives, such as 2-methylimidazole, 2-phenylimidazole, and
2-heptadecylimidazole; and also phosphines, tertiary amines, such
as benzylmethylamine and tris(dimethylaminomethyl)phenol, and also
metal soaps and acetylacetonates.
[0059] Examples of fillers and auxiliaries are expandable graphite,
boric acid, phosphoric esters, quartz, bolus alba (china clay),
chalk, wollastonite, talc, antimony trioxide, glass fibers, mineral
fibers, aluminum oxide, aluminum hydroxide, magnesium hydroxide,
precipitated silicas, silicates, and/or pulverized celluloses.
[0060] Blowing agents and nitrogen synergists are melamine and/or
guanidine and salts of these, and/or dicyandiamides. The melamine
salts are preferably melamine phosphate, melamine polyphosphate,
melamine cyanurate, melamine borate, melamine silicate, and the
guanidine salt is preferably guanidine phosphate.
[0061] As stated above, the inventive fire-protection coating which
forms an insulating layer may comprise from 0 to 60% by weight of
additives. Within this range of from 0 to 60% by weight, the
quantitative distribution of the additives may be as follows:
[0062] Accelerators: from 0 to 25% by weight, [0063] Fillers and
auxiliaries: from 0 to 100% by weight, [0064] Blowing agents and
nitrogen synergists: from 0 to 100% by weight, [0065] Carbon
donors: from 0 to 100% by weight, [0066] Pigments: from 0 to 50% by
weight, [0067] Flexibilizers: from 0 to 50% by weight, [0068]
Reactive diluents: from 0 to 25% by weight.
[0069] The percentage stated for each of the additives is therefore
based on the abovementioned 0 to 60% by weight as total.
[0070] The nitrogen-containing synergists are preferably those of
the formulae (III) to (VIII), or a mixture thereof ##STR3## [0071]
where [0072] R.sup.5 to R.sup.7 are hydrogen,
C.sub.1-C.sub.8-alkyl, or C.sub.5-C.sub.16-cycloalkyl or
-alkylcycloalkyl, optionally substituted with a hydroxy function or
with a C.sub.1-C.sub.4-- hydroxyalkyl function,
C.sub.2-C.sub.8-alkenyl, C.sub.1-C.sub.8-alkoxy, -acyl, -acyloxy,
C.sub.6-C.sub.12-aryl or -arylalkyl, --OR.sup.8 or
--N(R.sup.8)R.sup.9, including systems of alicyclic-N or aromatic-N
type, [0073] R.sup.8 is hydrogen, C.sub.1-C.sub.8-alkyl or
C.sub.5-C.sub.16-cycloalkyl or -alkylcycloalkyl, optionally
substituted with a hydroxy function or with a C.sub.1-C.sub.4--
hydroxyalkyl function, C.sub.2-C.sub.8-alkenyl,
C.sub.1-C.sub.8-alkoxy, -acyl, -acyloxy or C.sub.6-C.sub.12-aryl or
-arylalkyl, R.sup.9 to R.sup.13 are the groups of R.sup.8, or else
--O--R.sup.8, [0074] m and n, independently of one another, are 1,
2, 3, or 4, [0075] X is acids which can form adducts with triazine
compounds (III); or are oligomeric esters of tris(hydroxyethyl)
isocyanurate with aromatic polycarboxylic acids.
[0076] It is preferable that the nitrogen-containing synergists are
benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin,
glycoluril, melamine, melamine cyanurate, urea cyanurate,
dicyandiamide, guanidine.
[0077] It is preferable that the nitrogen synergists are
condensates of melamine. Examples of condensates of melamine are
melem, melam, or melon, or compounds of this type having a higher
condensation level, or else mixtures of the same, and by way of
example these can be prepared via a process described in
WO-A-96/16948.
[0078] The fire-protection coating which forms an insulating layer
preferably comprises carbohydrates as carbonizing substances.
[0079] Carbohydrates preferably used are pentaerythritol,
dipentaerythritol, tripentaerythritol, and/or polycondensates of
pentaerythritol.
[0080] Pigments which may be used are gas black, phthalocyanine
pigments, and metal oxides. Titanium dioxide is preferably used as
metal oxide.
[0081] To improve the toughness of the fire-protection coating,
butadiene-acrylonitrile rubber and other aliphatic polymers may be
added as flexibilizers.
[0082] Examples of reactive diluents which may be used are mono- or
polyhydric, low-molecular-weight alcohols which are reacted with
epichlorohydrin.
[0083] The epoxy resin used for the inventive fire-protection
coating is usually composed of an epoxy resin component and of a
hardener component.
[0084] Bisphenol A, bisphenol F, or a mixture of these is preferred
as epoxy resin component, and aliphatic amines are preferred as
hardener component.
[0085] The present object is likewise achieved via a process for
production of intumescent fire-protection coatings from epoxy
resins and from the abovementioned flame retardant mixture, which
comprises reacting an epoxy resin with the flame retardant mixture
and then converting it with a hardener into the fire-protection
coating.
[0086] The process can, if desired, also use solvents and diluents.
Aprotic polar solvents are preferred here. Examples here are:
N-methylpyrrolidone, dimethylformamide, ethers, such as diethyl
ether, tetrahydrofuran, dioxane, ethyl glycol ethers, propylene
glycol ethers, and butyl glycol ethers of monoalcohols having an
unbranched or branched alkyl radical of from 1 to 6 carbon
atoms.
[0087] Examples of other solvents which may be used are ketones,
such as acetone, methyl ethyl ketone, methyl isopropyl ketone,
methyl isobutyl ketone, cyclohexanone, and the like, and also
esters, such as ethyl acetate, butyl acetate, ethylene glycol
acetate, and methoxypropyl acetate. Other suitable solvents are
halogenated hydrocarbons, and cycloaliphatic and/or aromatic
hydrocarbons, preference being given here to hexane, heptane,
cyclohexane, toluene, and dixylenes. It is possible to use these
solvents individually or in a mixture.
[0088] The reaction of the epoxy resin with the flame retardant
mixture (component A+B) and with the hardener preferably takes
place at temperatures of -10 to +150.degree. C.
[0089] The invention likewise provides the use of the
abovementioned fire-protection coatings. These inventive
fire-protection coatings are preferably used for coating
load-bearing and non-load-bearing metallic structures or forms. The
inventive fire-protection coatings can also be used to protect
floorcoverings, walls, or moldings from stresses caused by
temperature.
[0090] The inventive fire-protection coatings have good flame
retardancy and are simple to process. The preferred method here
mixes the epoxy resin and the hardener components, or the
constituents which comprise them, shortly prior to application. In
another preferred method, the systems comprising the epoxy resin
and the systems comprising the hardener components are heated
slightly in order to reduce viscosity. This simplifies spray
application--preferably by the airless method. Typically, the
systems to be heated are heated to from 50.degree. C. to 75.degree.
C., and the temperature of the systems to be heated should
preferably be from 65.degree. C. to 70.degree. C. directly prior to
application.
[0091] In the following examples, intumescent fire-protection
coatings are produced and their effectiveness is determined. The
thermal insulation capability of the intumescent fire-protection
coatings was tested in a small test rig by analogy with DIN4102
Part 8 (1986), using the heating curve by analogy with ISO834
(1975). Thermogravimetric evaluation of the flame retardant mixture
was carried by an analytical method using a "NETZSCH STA 409C"
thermal balance.
EXAMPLES 1 to 5
[0092] The following products were used in the examples:
.RTM.Exolit AP422 (Clariant GmbH)
[0093] .RTM.Exolit AP422 is a free-flowing, pulverulent ammonium
polyphosphate of the formula (NH.sub.4PO.sub.3).sub.n, where n=from
20 to 1000, in particular from 200-1000, which is sparingly soluble
in water.
.RTM.Exolit AP750 (Clariant GmbH)
[0094] This is a halogen-free flame retardant mixture which
comprises polymeric ammonium polyphosphate in combination with
aromatic carboxylic esters of tris(2-hydroxyethyl) isocyanurate as
synergists.
.RTM.Exolit OP1230 (Clariant GmbH)
[0095] .RTM.Exolit OP1230 is a fine-grained, non-hygroscopic powder
based on an organic phosphinate and insoluble in water and in
familiar organic solvents.
.RTM.Beckopox EP140 (UCB-Surface Specialties)
[0096] This is a low-molecular-weight condensate composed of
bisphenol A and epichlorohydrin with density of 1.16 g/ml (at
25.degree. C.) and with an epoxy equivalent weight of from
180-190.
.RTM.Beckopox EH624 (UCB-Surface Specialties)
[0097] This is an aliphatic polyamine whose active-H equivalent
weight is 80 g/mol, with a dynamic viscosity of from 2300-3800 mPas
(at 23.degree. C.).
Tronox.RTM. R-KB-5 (Kerr Mc-Gee Chemical LLC)
[0098] This is a rutile-type titanium dioxide which was stabilized
with Al.sub.2O.sub.3, and the surface was treated with Al
components and with Zr components.
Optibor.RTM. Boric Acid (Deutsche Borax GmbH)
[0099] This is a pure boric acid of the formula
(H.sub.3BO.sub.3)
Example 1
Comparison
[0100] 100 parts of Beckopox EP 140, 25 parts of boric acid, 2
parts of TiO.sub.2, and 100 parts of Exolit AP422 were introduced
in succession in a stirred vessel and, after adequate mixing,
reacted with 43 parts of Beckopox EH 624. The resultant
fire-protection coating was applied to one side of a steel plate
(St 37) measuring 280.times.280.times.6 mm, using a roller. The
composition cured for one day at room temperature, and its layer
thickness was determined as 3.5 mm.
[0101] The surface of the coating was smooth and free from
cracks.
[0102] The fire test on the coated sheet to DIN 4102 gave a fire
resistance of 33 minutes. The reaction started at T=240.degree.
C.
Example 2
Comparison
[0103] The fire-protection coating used was the same as that used
in Example 1, but Exolit AP750 was used instead of Exolit AP422.
The resultant fire-protection coating was applied to one side of a
steel plate (St 37) measuring 280.times.280.times.6 mm, using a
roller. The composition cured for one day at room temperature, and
its layer thickness was determined as 3.5 mm.
[0104] The surface of the coating was smooth and free from
cracks.
[0105] The fire test on the coated sheet to DIN 4102 gave a fire
resistance of 41 minutes. The reaction started at T=220.degree.
C.
Example 3
Invention
[0106] 100 parts of Beckopox EP 140, 25 parts of boric acid, 9
parts of tris(hydroxyethyl) isocyanurate, 2 parts of TiO.sub.2, and
5 parts of a disparate flame retardant mixture composed of Exolit
AP422 and Exolit OP1230 were introduced in a stirred vesssel and,
after adequate mixing, reacted with 43 parts of Beckopox EH 624.
The resultant fire-protection coating was applied to one side of a
steel plate (St 37) measuring 280.times.280.times.6 mm, using a
roller. The composition cured for one day at room temperature, and
its layer thickness was determined as 3.5 mm.
[0107] The surface of the coating was smooth and free from
cracks.
[0108] The fire test on the coated sheet to DIN 4102 gave a fire
resistance of 44 minutes. The reaction started at T=179.degree.
C.
Example 4
Erfindung
[0109] 100 parts of Beckopox EP 140, 25 parts of boric acid, 9
parts of tris(hydroxyethyl) isocyanurate, 2 parts of TiO.sub.2, and
60 parts of a disparate flame retardant mixture composed of Exolit
AP422 and Exolit OP1230 were introduced in a stirred vesssel and,
after adequate mixing, reacted with 43 parts of Beckopox EH 624.
The resultant fire-protection coating was applied to one side of a
steel plate (St 37) measuring 280.times.280.times.6 mm, using a
roller. The composition cured for one day at room temperature, and
its layer thickness was determined as 3.5 mm.
[0110] The surface of the coating was smooth and free from
cracks.
[0111] The fire test on the coated sheet to DIN 4102 gave a fire
resistance of 49 minutes. The reaction started at T=175.degree.
C.
Example 5
[0112] 100 parts of Beckopox EP 140, 25 parts of boric acid, 9
parts of tris(hydroxyethyl) isocyanurate, 2 parts of TiO.sub.2, and
140 parts of a disparate flame retardant mixture composed of Exolit
AP422 and Exolit OP1230 were introduced in a stirred vesssel and,
after adequate mixing, reacted with 43 parts of Beckopox EH 624.
The resultant fire-protection coating was applied to one side of a
steel plate (St 37) measuring 280.times.280.times.6 mm, using a
roller. The composition cured for one day at room temperature, and
its layer thickness was determined as 3.5 mm.
[0113] The surface of the coating was smooth and free from
cracks.
[0114] The fire test on the coated sheets to DIN 4102 gave a fire
resistance of 59 minutes. The reaction started at T=164.degree.
C.
Example 6
[0115] The fire-protection coating produced was the same as that
produced in Example 5, but the application thickness was 2.0 mm.
The surface of the coating was smooth and free from cracks.
[0116] The fire test on the coated sheet to DIN 4102 gave a fire
resistance of 42 minutes. The reaction started at T=166.degree.
C.
Example 7
Invention
[0117] The flame retardant mixture from Examples 3 and 4, and also
the individual components Exolit AP422 and Exolit OP1230 present
therein, were compared thermogravimetrically. The significantly
earlier start of the reaction of the flame retardant mixture shows
the synergy when comparison is made with the individual components
(FIG. 1).
* * * * *